Method for extending shelf life of juice

ABSTRACT

A composite barrier laminate for a carton for citrus juices that extends the shelf life of the citrus juice by inhibiting the proliferation of microbial growth therein. The composite barrier laminate has a plurality of layers with one layer being a thin barrier skin coat in contact with the juice, The skin coat is impervious to the antimicrobial agent D-limonene and is effective to prevent the migration of the D-limonene found in the citrus juice. A method for extending the shelf life of a citrus juice stored in a paperboard carton for preventing the D-limonene present in the citrus juice stored in a carton from migrating into the carton structure by making the innermost layer of the carton impervious to D-limonene is disclosed as is a method for preserving the antimicrobial properties present in a citrus juice that is stored in a paperboard carton formed from a laminate by preventing migration of D-limonene from the citrus juice into the laminate by making the innermost layer impervious to D-limonene.

RELATED APPLICATION

This application is a continuation-in-part of application Ser. No.775,017, filed Oct. 11, 1991, issued to U.S. Pat. No. 5,175,036 .

BACKGROUND OF THE INVENTION

The present invention relates to a composite barrier laminate for acarton for citrus beverages including juices and other liquids. Moreparticularly, it relates to a composite barrier laminate for a cartonfor citrus juices that extends the shelf life of the citrus juice byinhibiting the proliferation or growth of microorganisms. The compositebarrier laminate has a barrier skin coat layer that is impervious to theantimicrobial agent D-limonene so that it prevents the migration ofD-limonene from the citrus juice.

The present invention also relates to a method for extending the shelflife of a citrus juice stored in a paperboard carton. The methodcomprises preventing the antimicrobial agent D-limonene present in thecitrus juice stored in the carton from migrating into the cartonstructure by making the innermost layer of the carton structureimpervious to D-limonene. The present invention provides a method forpreserving the antimicrobial properties present in citrus juice that isstored in a paperboard carton or container by preventing the migrationof D-limonene from the citrus juice by storing the citrus juice in acarton formed from a laminate having an innermost layer that isimpervious to D-limonene.

The prior art believed that flavor degradation in citrus juice and othercitrus beverages during storage in the preferred polyethylene coatedcartons was caused by the loss of essential "flavor" oils. Accordingly,laminate structures that prevent the loss of "flavor" oils in order toavoid flavor degradation are now known in the art.

The present invention unexpectedly found that with the growth ofmicroorganisms, such as, for example, yeast, mold and bacteria, flavorchanges or defects in a citrus juice occur. The present invention alsofound that D-limonene in citrus juices, such as orange juice, acts as astrong antimicrobial agent that inhibits the proliferation ofmicroorganisms which, in turn, extends the shelf life of the juice. Itis believed that when D-limonene migrates into and is absorbed in thepolyethylene coating of a carton, the microbial growth in the citrusjuice after eight weeks can be one hundred times greater than itsinitial condition.

Heretofore, the useful shelf life of a citrus juice has been limited toa few weeks. It is now believed that the principal reasons are flavorloss due to microbial growth and loss of nutritional value due to theoxidation of ascorbic acid (vitamin C) below the regulation level of 30mg ascorbic acid per 100 ml. The loss of ascorbic acid can be preventedfor seven or eight weeks by using oxygen barrier layers such aspolyamide, ethylene vinyl alcohol (EVOH) or polyethylene terephthalate(PET). Nevertheless, whether the juice is held in non-oxygen barrier oroxygen barrier cartons, flavor loss can become noticeable within abouttwo weeks because as much as thirty percent of the D-limonene in thecitrus juice may be absorbed into the heat seal coating layer within afew days. This is known as scalping.

Glass containers and molded plastic containers have been used to storeand transport juice. However, both have a number of disadvantages,including shipping costs for the empty containers, disposal problems,breakage and weight problems.

To obtain the advantages of comparatively low container weight, ease ofsealing and opening, ease of disposal and low shipping volume for emptycontainers, since such containers can be shipped in a collapsedcondition, containers based on a paperboard substrate are the currentchoice for marketing citrus juice and other products. These cartons areknown in the trade as "gable top" containers or cartons. Such a cartonis described in U.S. Pat. No. 3,120,333. These gable top cartons use lowdensity polyethylene as the preferred food-contact polymer.

It has, however, been found that low density polyethylene (LDPE) has avery high absorption and migration capacity for D-limonene. Unless aD-limonene barrier layer is part of the container construction,migration can result in as much as a 60% loss of D-limonene before theexpiration of the container's sale date.

The prior art has provided laminates having a metal foil layer to retainthe vitamin content and flavors in the juice for a substantial period oftime, about ten weeks. The skin coat layer is not, however, the metalfoil layer. Also, these laminates do not address the issue of inhibitingthe migration or the resultant loss of the antimicrobial agent from thecitrus juice. Further, metal foil laminate containers are expensive whencompared to non-metal foil laminate containers, and are prone to developpin holes that seriously affect their ability to contain liquids.

While considerable efforts have been devoted to finding the best layerstructure in a barrier laminate, such efforts have failed to appreciatethe superior and unexpected results of longer shelf life which isachieved by providing a thin skin coat layer that is impervious toD-limonene to prevent the migration of D-limonene from the citrus juice.

For example, U.S. Pat. No. 4,513,036 describes a laminate useful inmaking a paperboard based carton for juices, that provides an effectivebarrier to the migration of essential oils and/or flavors, and does notcontain a metal foil. This laminate has a paperboard substrate, apolypropylene polymer layer coated thereon and a polyolefin layerapplied onto the polypropylene polymer layer.

A laminate that provides an effective barrier to oxygen and, thus, helpsretain vitamin C in the juice stored in the carton is described in U.S.Pat. No. 4,777,088. This laminate comprises from the outer surface tothe inner surface which would contact the juice, a paperboard substrate,a nylon layer coated directly on the paperboard substrate, a layer ofpoly(ethylene-co-methacrylic acid) partially neutralized with sodium andzinc cations (Surlyn) directly overlying and in contact with the nylonlayer, and an inner polyolefin layer in contact with the Surlyn layer.The nylon barrier layer helps retain vitamin C and, in addition,essential oils and flavor as does the laminate in U.S. Pat. No.4,513,036.

Likewise, other barrier laminates that are capable of excluding oxygenand preventing the loss of oils and/or flavors are described in U.S.Pat. Nos. 4,977,004, 4,977,009, 4,950,510, 4,861,526, 4,835,025,4,806,399, 4,753,832, 4,701,360 and 4,698,246. In U.S. Pat. Nos.4,701,360, 4,861,526 and 4,698,246, both sides of a paperboard substrateare first flame treated and a layer of low density polyethylene isapplied to the outside surface. To the surface of the paperboard thatbecomes the inside surface of the carton, a layer of low, densitypolyethylene is initially applied directly to the paperboard, followedby a nylon barrier layer that is applied to that interior low densitypolyethylene layer with a bonding tie layer between the nylon and thepolyethylene. Lastly, an innermost skin layer is applied to the nylonwith another tie layer to improve the adhesion of the layers and to helpin heat sealing. This skin layer is made of ethylene vinyl alcoholcopolymer.

U.S. Pat. No. 4,948,640 provides five embodiments for a heat sealablebarrier laminate. Each embodiment provides a substantial barrier to lossof vitamin C over an extended shelf life of the carton, namely abouteight weeks. Each embodiment further provides that the skin coat layeris a thin layer of a low density polyethylene polymer.

Not one of these patents recognizes that the cause of flavor degradationin citrus juice, such as orange juice, is the proliferation ofmicrobiological organisms or microorganisms that occurs when theD-limonene migrates out of the juice. Accordingly, these patents fail toprovide a method for inhibiting the loss of the antimicrobial agent inthe citrus juice contained in the carton or, moreover, appreciate that asubstantial increase in shelf life can be accomplished by inhibiting theproliferation of the microorganisms by providing an innermost layer thatis made of a material impervious to the antimicrobial agent D-limonenethereby retarding the loss of D-limonene from the citrus juice.

Thus, the present invention provides a barrier skin coat that willprevent the migration or loss of D-limonene from the citrus juice,inhibit the growth of microorganisms, and the rapid loss of flavor duethe the growth of microorganisms.

SUMMARY OF THE INVENTION

Against the foregoing background, it is a primary object of the presentinvention to provide a comparatively economical barrier laminate for acarton for a citrus juice including citrus juice and other liquids thatimproves the shelf life of the citrus juice by inhibiting theproliferation microorganisms.

It is another object of the present invention to provide such acomparatively economical barrier laminate or a carton for a citrus juicethat prevents the loss of the antimicrobial agent D-limonene found inthe citrus juice by employing a thin barrier or skin layer effective toprevent the migration of D-limonene in the laminate in which the barrierlayer contacts the juice contained in the carton.

It is a further object of the present invention to provide laminates forjuice cartons having such a skin layer that, in the absence of an oxygenbarrier layer it, the barrier laminate, also functions as a limitedoxygen barrier.

It is a still further object of the present invention to providelaminates for juice cartons having such a limited oxygen barrier skinlayer that retards the loss vitamin C (ascorbic acid) due to oxidation.

It is yet a further object of the present invention to provide a juicecarton constructed of a laminate effective to prevent the migration ofD-limonene from the juice into the carton structure.

It is yet another object of the present invention to provide a methodfor extending the shelf life of a citrus juice stored in a paperboardcarton by preventing the antimicrobial agent D-limonene present in thecitrus juice from migrating into the carton structure by making theinnermost layer of the carton structure impervious to D-limonene.

It is yet still another object of the present invention to provide amethod for preserving the antimicrobial properties present in a citrusjuice that is stored in a paperboard container by preventing migrationof the antimicrobial agent D-limonene from the citrus juice by storingthe citrus juice in a container formed from a laminate having an innermost layer that is impervious to D-limonene.

According to the present invention, the laminate providing an effectivebarrier to the migration D-limonene from the juice comprises from theouter paperboard surface to the inner surface contacting the juice: apaperboard substrate, a nylon barrier layer contacting the paperboardsubstrate directly, a first tie layer, a polyethylene heat seal layer, asecond tie layer, and an inner skin layer that comes in contact with thefruit juice or contents of the carton made from the laminate. The firsttie layer adheres the polyethylene heat seal layer to the nylon layer.The second tie layer adheres the inner skin layer to the polyethyleneheat seal layer.

The inner skin layer is preferably made of material selected from thegroup consisting of polyamide (nylon), copolyamide, ethylene vinylalcohol copolymer (EVOH) and polyethylene terephthalate (PET).

Advantageously, the outer surface of the paperboard substrate isprovided with a low density polyethyl layer which provides a means forheat sealing the flaps of the cartons made from this laminate.

The comparatively economical laminate of the present invention hasoutstanding oxygen barrier properties. A citrus fruit juice contained ina carton made from this laminate loses no more than 20 to 25 percent ofits vitamin C content in eight weeks.

Because of the failure of D-limonene to rate, the antimicrobialproperties of this juice are preserved contributing greatly to itsenhanced shelf life. This finding that D-limonene is possessed ofantimicrobial properties is attributable to applicants.

BRIEF DESCRIPTION OF THE DRAWINGS

The foregoing and still other objects and advantages of the presentinvention will be more apparent from the following detailed explanationof the preferred embodiments of the invention in connection with theaccompanying drawings wherein:

FIG. 1 is a perspective view with the layers separated at one end of afirst preferred barrier laminate of the present invention;

FIG. 2 is a cross-sectional view of the laminate of FIG. 1; and

FIG. 3 is a cross-sectional view of the structure of a second preferredbarrier laminate of the present invention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

The present invention provides that the innermost layer in a citrusjuice carton or container must be impervious to the antimicrobial agentD-limonene in order to prevent or inhibit the loss or migration of theD-limonene from the citrus juice into the layers of the carton. Bylimiting the loss of the antimicrobial agent D-limonene from the citrusjuice, it has unexpectedly been found that the flavor of the citrusjuice is maintained for a substantially longer period of time therebycorrespondingly enhancing the shelf life of the citrus juice.

A citrus juice as defined in this application includes all citrusjuices, including orange juice and other liquids. The innermost layer ofthe carton or container is known as the "skin" or "skin coat" layer. Itis the layer of the composite barrier laminate that contacts the juicein the carton.

It has been found as illustrated in the test results set forth in thisapplication that by preventing the antimicrobial agent D-limonenepresent in the citrus juice stored in a carton from migrating into thecarton structure, the flavor of the citrus juice can be maintainedlonger, thereby enhancing the shelf life of the juice.

The preferred materials that have been found to be impervious toD-limonene are polyamide (nylon), copolyamide, ethylene vinyl alcoholcopolymer (EVOH) and polyethylene terephthalate. As discussed below,other materials, namely, PETG and polycarbonate, are impervious toD-limonene and, therefore, can be used as the skin coat layer in thepresent composite barrier laminate. The present invention may bepracticed using a skin layer made of these materials in combination witha variety of different substrate, barrier, tie and heat seal layers asalso set forth below.

Referring to the drawings and, in particular, FIGS. 1 and 2, there isprovided a first preferred barrier laminate of the present inventiongenerally represented by reference numeral 1. The barrier laminate 1comprises a plurality of layers.

In particular, the barrier laminate 1 includes, in the following orderfrom the outermost layer to the innermost or skin layer, a substrate orbase layer 10 having a first or interior surface and a second orexterior surface. There is applied directly to the first surface of thesubstrate 10, a barrier layer 20. A first tie layer 30 is applieddirectly to the barrier layer 20, and then a heat seal layer 40 isapplied to the first tie layer. Also, a second tie layer 50 is appliedto the heat seal layer 40, and a skin or skin coat layer 60 is appliedto the second tie layer. In addition, there is preferably applieddirectly onto the second or exterior surface of the base layer an outeror exterior layer 5.

The exterior layer 5 provides a print surface for a graphics panel. Inaddition, the exterior layer 5 provides an outer heat seal medium forbonding the carton flaps together and effecting the top and bottom heatseals. The exterior heat seal layer 5 is an olefin polymer and,preferably, is made of polyethylene. In the most preferred embodiment,the exterior heat seal layer 5 is a low density polyethylene. The lowdensity polyethylene layer 5 has a weight of about sixteen (16) poundsper ream.

The substrate 10 provides the barrier laminate 1 with structure, form,strength and rigidity so that the barrier laminate can be formed into acarton. The substrate 10 is composed of a paperboard, preferably asuitable high-grade paperboard. For example, the paperboard substrate 10could be about 0.010 inches to about 0.028 inches carton stock. In thispreferred embodiment, the paperboard is a bleached sulfate paperboard.This material has a basis weight of about one hundred and ninety-five(195) to about two hundred and eighty (280) pounds per ream.

The barrier layer 20 is applied directly onto the paperboard substrate10 and especially functions as a barrier to oxygen. In this embodiment,the barrier layer 20 is made of a polyamide and is applied directly tothe paperboard substrate. This barrier layer 20 is responsible for thebarrier laminate's effectiveness in preventing the intrusion of oxygento the inside of the carton or container. This barrier layer has acoating weight of about three (3) to about five (5) pounds per ream.

The first tie layer 30 is positioned immediately adjacent to and betweenthe barrier layer 20 and the heat seal layer 40 to adhere together thebarrier layer and the heat seal layer. The first tie layer 30 is applieddirectly onto the barrier layer 20 after the barrier layer has beendirectly applied onto the paperboard substrate 10.

The first tie layer 30 is preferably made of Bynel E 388 which ismarketed by DuPont. The Bynel E 388 first tie layer has a coating weightof about three (3) to about five (5) pounds per ream.

The heat seal layer 40 provides the heat seal bonds that define thestructure of the carton. This heat seal layer 40 also provides theliquid tight and gas tight closures of the carton. The heat seal layer40 is a heat sealable olefin polymer. It is preferably polyethylene, andmost preferably a low density polyethylene. The low density polyethylenehas a coating weight of about sixteen (16) pounds per ream.

The second tie layer 50 is positioned immediately adjacent to andbetween the heat seal layer 40 and the skin layer 60. Like the first tielayer 30, the second tie layer 50 functions to adhere together the twoadjacent layers, namely the heat seal layer 40 and the skin layer 60.This second tie layer 50, like the first tie layer 30, is preferablymade of Bynel E 388. Bynel E 388 is a modified polyethylene resin and ismarketed by DuPont. Bynel E 388 has a coating weight of about three (3)to about five (5) pounds per ream. In the second tie layer 50, Plexar175 can be substituted for Bynel E 388. Plexar 175 is a low densitypolyethylene based tie layer, and is marketed by Quantum corp.

Bynel E 369, which is also marketed by DuPont, can be used as the secondtie layer 50. Bynel E 369 is a modified low density polyethylene basedadhesive resin. It is preferred that Bynel E 369 be used as the secondtie layer material if the skin layer is made of polyethyleneterephthalate.

The skin layer 60 is the innermost layer of the carton and, therefore,it contacts the beverage or food in the carton. In the present inventionthe skin layer 60 functions to prevent the migration of theantimicrobial agent D-limonene from the citrus juice into thepolyethylene heat seal layer 40.

The skin layer 60 is a very thin layer. The skin layer 60, preferably,is made of a polyamide (nylon). However, the skin layer 60 can be madeof copolyamide, polyethylene terephthalate or ethylene vinyl alcoholcopolymer. The skin layer 60 has a coating weight of about three (3) toabout (4) pounds per ream.

As stated above, if the skin layer 60 is made of polyethyleneterephthalate, the second tie layer 50 is preferably made of Bynel E369.

The skin layer 60 material is not heat sealable. Therefore, the cartonside flap, bottom flaps and top seals are formed by applying heat in theform of hot air and closing pressure so that the thin skin layer 60 andthe adjacent, thicker low density polyethylene layer become molten andflow together in such a manner that that portion of the skin layer 60 isdiluted and does not interfere with the heat seal between thepolyethylene heat seal layer 40 and the exterior polyethylene seal layer5.

Therefore, a typical carton made of the barrier laminate of the presentinvention should have a low density polyethylene outer layer 5 with acoating weight of about 16 pounds per ream, a bleached sulfatepaperboard base layer with a basis weight of about 195 to about 280pounds per ream, a nylon barrier layer with a coating weight of about 5pounds per ream, a modified polyethylene (Bynel E - 388) first tie layerwith a coating weight of about 3 to about 5 pounds per ream, a lowdensity polyethylene heat seal layer with a coating weight of about 16pounds per ream, a modified polyethylene (Bynel E - 388) second tielayer with a coating weight of about 3 to about 5 pounds per ream, and askin layer with a coating weight of about 3 to about 4 pounds per reammade from either a polyamide, copolyamide, polyethylene terephthalate oran ethylene vinyl alcohol copolymer.

The paperboard and polymer laminate functions as a carton forcontaining, storing, transporting and dispersing fruit juices, fruitbeverage and other beverages and is particularly adapted to thoseinstances that require prevention of microbial growth and migration ofD-limonene from the juice into the container structure, resulting in alonger shelf life and a higher quality of product. The laminate barrieras just described has an oxygen barrier that prevents the intrusion ofoxygen and resulting loss of ascorbic acid or vitamin C. This latterfeature is advantageous since it assists in complying with State andFederal regulations involving citrus juices reconstituted from thefrozen concentrate. Another advantage of the laminate barrier is that ithas a "skin coat" barrier, namely layer 60, that prevents the absorptionof essential oils and flavors into the polyethylene heat seal layer 40so that flavor components of the juices do not change.

In addition, the heat seal layer 40 provides heat seal bonds that definethe structure of the carton and provide liquid and gas tight closures.

Thus, the present barrier laminate provides all the desired propertiesfor a paperboard juice carton.

In the second embodiment shown in FIG. 3, the barrier laminate 100comprises an outer heat seal layer 110 applied onto a paperboard layer120, a heat seal layer 130 applied to the outer surface of thepaperboard layer, a tie layer 140 applied to the heat seal layer, and askin layer 150 applied to the tie layer.

In the second embodiment, the outer seal layer 110 provides a printsurface for a graphics panel. The outer seal layer 110 is made of lowdensity polyethylene (LDPE) that has a coating weight of about 16 poundsper ream. The paperboard layer 120 is a bleached sulfate paperboardsubstrate that has a basis weight of about 195 to about 280 pounds perream. The heat seal layer 130 is made of low density polyethylene. It,like the outer seal layer 110, has a coating weight of about 16 poundsper ream. The tie layer 140 is made of Bynel E 388 and has a coatingweight of three to five pounds per ream. In this embodiment, the skin orinnermost layer 150 is made of polyamide. The polyamide skin layer 150has a coating weight of about 3 to about 4 pounds per ream.

In an alternative to the second embodiment, the barrier laminate 100also comprises a low density polyethylene outer heat seal layer 110 thathas a coating weight of about 16 pounds per ream, a bleached sulfatepaperboard substrate layer 120 that has a basis weight of about 195 toabout 280 pounds per ream, a low density polyethylene heat seal layer130 that has a coating weight of about 16 pounds per ream, a tie layer140 that has a coating weight of about 3 to about 5 pounds, and a skinlayer 150 that has a coating weight of about 3 to about 4 pounds perream. However in this alternative second embodiment, the skin coat layer150 is made of ethylene vinyl alcohol, instead of polyamide.

In the second embodiment, the skin coat layer 150 also serves as alimited oxygen barrier layer.

As stated above, it is anticipated that in all embodiments of thelaminate, the skin coat layer can be PETG, polycarbonate or copolyamideinstead of a polyamide, EVOH or PET. It is also anticipated that thelaminate could consist of the following alternatives from the outerlayer to the inner layer contacting the juice:

    __________________________________________________________________________    LDPE    LDPE    LDPE/EVOH                                                                             LDPE/EVOH                                                                             LDPE    LDPE                                  BOARD   BOARD   BOARD   BOARD   BOARD   BOARD                                 LDPE    LDPE    LDPE    LDPE    LDPE    LDPE                                  POLYAMIDE                                                                             TIE     POLYAMIDE                                                                             TIE     TIE     TIE                                           POLYAMIDE       POLYAMIDE                                                                             FOIL    PET                                                                   TIE     TIE                                                                   POLYAMIDE                                                                             POLYAMIDE                             LDPE    LDPE    LDPE    LDPE    LDPE    LDPE    LDPE                          BOARD   BOARD   BOARD   BOARD   BOARD   BOARD   BOARD                         LDPE    POLYAMIDE                                                                             TIE     TIE     LDPE    PET     TIE                           TIE     TIE     POLYAMIDE                                                                             EVOH    TIE     TIE     PET                           PETG    LDPE    TIE     TIE     PVDC    LDPE    TIE                           TIE     TIE     LDPE    LDPE    TIE     TIE     LDPE                          POLYAMIDE                                                                             POLYAMIDE                                                                             TIE     TIE     POLYAMIDE                                                                             POLYAMIDE                                                                             TIE                                           POLYAMIDE                                                                             POLYAMIDE               POLYAMIDE                     __________________________________________________________________________

By making the thin skin layer impervious to D-limonene, the loss ofantimicrobial properties is substantially reduced resulting in a longershelf life and a higher quality product. Also, the skin layer has beenfound to reduce the access of oxygen thereby slowing the loss ofascorbic acid.

In addition, the present barrier laminate, by use of the heat seallayer, provides heat seal bonds that define the structure of the cartonand provide liquid tight and gas tight closures. Thus, as already noted,the present barrier laminate provides all the desired properties for apaperboard type beverage carton.

COMPARATIVE TESTS

In order to determine the effect of different skin. layers of laminateson the retention of ascorbic acid and D-limonene in orange Juice, aseries of tests were carried out. Cartons in accordance with thelaminate of the first embodiment of the present invention were prepareddiffering only in their innermost or skin layer, the layer which in usewould contact the juice contents. Cartons corresponding to theconventional or regular polyethylene carton were also prepared, and wereconsidered the control cartons.

The conventional test methods for carrying out the studies and theanalytical procedures were used.

Orange juice, filled at an operational juice plant, was packaged andstored in the following half gallon cartons for eight (8) weeks:

1. Regular PE

2. Invention/EVOH

3. Invention/POLYAMIDE (NYLON)

4. Invention/PET

All cartons were filled with orange juice, sealed, refrigerated and thentested for the retention of D-limonene and ascorbic acid in the juiceover an eight week period by standard AOAC methods in the same manner asin U.S. Pat. No. 4,777,088.

Results and Discussion

The results discussed below are confined mainly to the first six weeks.After that time, the presence of mold and other microbial growth wouldbe a factor influencing the continued degradation of orange juice. Moldwas observed after six weeks, much of the observed mold being located oncarton seams where oxygen would have encouraged growth. Microbial growthwas likely to have been present several days before physical observationthereof.

D-LIMONENE

Invention/PET and Invention/EVOH

The orange juice contained in these cartons retained close to 100% ofD-limonene, which is characteristic of these non-scalping polymers.

Invention/POLYAMIDE (NYLON)

The orange juice contained in these cartons lost about 8-9% D-limoneneby week 2, after which time it seemed to stabilize at about 91%retention.

Regular PE

The orange juice in the regular PE cartons continued a downward loss ofD-limonene. At week 6, retention was less than 60%.

ASCORBIC ACID

Invention/EVOH and Invention/POLYAMIDE (NYLON)

The orange juice in these cartons showed similar trends in the loss ofascorbic acid. By week 6, both of these cartons had maintainedapproximately 78% retention.

Invention/PET

These cartons showed a slightly lower percent retention than the otherstructures. At week 6, ascorbic acid retention was 70%. It was observedthat the PET carton had poor side, top and bottom seams, which may haveallowed for greater oxidation of ascorbic acid.

Regular PE

Orange juice in the regular PE carton showed a continued drop inascorbic acid retention weekly. At week 6, the ascorbic acid retentionwas only 25%.

Following week 6, the effect of microbial growth in the juice may havecontributed to the decrease in ascorbic acid retention.

The average data from the chemical analysis is presented below:

                                      TABLE 1                                     __________________________________________________________________________    % D-LIMONENE RETENTION                                                        WEEK                                                                          SAMPLE                                                                              0  1   2   3   4   5   6   7   8                                        __________________________________________________________________________    PE    100.0                                                                            91.18                                                                             77.65                                                                             73.53                                                                             68.24                                                                             60.35                                                                             57.65                                                                             47.06                                                                             49.76                                    EVOH  100.0                                                                            100.00                                                                            100.00                                                                            100.00                                                                            100.00                                                                            100.00                                                                            100.00                                                                            100.00                                                                            100.00                                   NYLON 100.0                                                                            96.67                                                                             91.11                                                                             92.22                                                                             92.78                                                                             93.33                                                                             93.33                                                                             86.67                                                                             86.22                                    PET   100.0                                                                            100.00                                                                            100.00                                                                            100.00                                                                            100.00                                                                            100.00                                                                            100.00                                                                            100.00                                                                            100.00                                   __________________________________________________________________________

                                      TABLE 2                                     __________________________________________________________________________    % ASCORBIC ACID RETENTION                                                     WEEK                                                                          SAMPLE                                                                              0   1  2   3  4   5   6   7  8                                          __________________________________________________________________________    PE    100.0                                                                             86.67                                                                            75.85                                                                             62.85                                                                            53.13                                                                             40.92                                                                             24.77                                                                             10.77                                                                             7.96                                      EVOH  100.0                                                                             93.52                                                                            88.95                                                                             89.40                                                                            81.21                                                                             80.00                                                                             78.92                                                                             71.31                                                                            71.50                                      NYLON 100.0                                                                             93.76                                                                            87.56                                                                             88.37                                                                            80.02                                                                             80.97                                                                             77.77                                                                             69.67                                                                            70.46                                      PET   100.0                                                                             92.17                                                                            85.77                                                                             84.97                                                                            77.51                                                                             76.61                                                                             70.18                                                                             63.33                                                                            62.98                                      __________________________________________________________________________

As shown in the tabular and graphic results set forth in Table 1, orangejuice packaged in EVOH and PET skin coated cartons retained 100% of theD-limonene content through week 8. The regular polyethylene juice cartonwas shown to be an inferior structure for retention of D-limonene. Asshown in tabular and the graphic results set forth in Table 2, theorange juice packaged in EVOH, PET and POLYAMIDE (NYLON) cartonsretained approximately 75% of its ascorbic acid content through week sixand the regular polyethylene juice carton was also shown to be aninferior structure for retention of ascorbic acid.

Summary

Orange juice contained in various skin coated cartons was chemicallyanalyzed for retention of ascorbic acid and D-limonene over an eightweek period. Orange juice packaged in cartons in accordance with thefirst embodiment of the present invention retained approximately 75% ofits ascorbic acid content through week six. Orange juice packaged inEVOH and PET skin coat cartons retained 100% of the D-limonene contentthrough week 8. The regular polyethylene juice carton was shown to be aninferior structure for retention of either ascorbic acid or D-limonene.

Laboratory tests were made to illustrate the effect of pure D-limoneneon microbial counts. In a first approach, juice from a single lot ofconcentrate was made to different oil contents. The range covered thelegal grade A limits for orange juice (0.011 to 0.035%). The juices wereheld at 4 degrees C in hydrogen peroxide sterilized gable top cartonswith LDPE skin coats. Plate counts were taken biweekly for the first twoweeks and weekly thereafter. The effect of peel oil on microbial numberswas studied, and peel oil and ascorbic acid were monitored. Thisapproach examined the container/microbiological relationship underactual conditions of container use.

In the second approach, LDPE strips were added to the juices held innitrogen-purged glass vessels. Identically treated juice without a LDPEsheet served as the control. The juices were monitored microbially asdescribed above, and peel oil and ascorbic acid were also monitored.This approach removed potential deviations dictated by variable-oxygenpermeabilities.

The results of microbial growth versus percent D-limonene in OSA plates(average count) are set forth in the following chart and graphic resultsin Tables III, and the results of microbial growth versus percentD-limonene in APDA plates (average count) are set forth in the followingchart and graphic results in Tables IV. Also, the results of themicrobial growth versus percent peel oil in OSA plates (average count)and in APDA plates (average count) are set forth graphically in thefollowing Tables V and VI, respectively.

                                      TABLE III                                   __________________________________________________________________________    THE EFFECT OF PURE LIMONENE ON MICROBIAL COUNTS                               RUN NUMBER 2       INCUBATION TEMPERATURE 40 DEGREES F.                       OIL LEVEL .001 (CONTROL)                                                                         DATE PUT INTO STORAGE 6/25/91                                    TIME                                                                              SAMPLE        DUPLICATE    AVE. +/- SD                              DATE  IN  COUNTS        COUNTS       LOG                                      PLATED                                                                              DAYS                                                                              OSA       LOG OSA      LOG CFU                                      __________________________________________________________________________    6/25  0   22.00 × 10 - 1*                                                                   2.34                                                                              20.00 × 10 - 1*                                                                  2.30                                                                              2.33/0.019                                         21.00 × 10 - 1*                                                                   2.32                                                                              22.00 × 10 - 1*                                                                  2.34                                         6/26  1   16.00 × 10 - 1*                                                                   2.20                                                                              23.00 × 10 - 1*                                                                  2.36                                                                              2.28/0.113                               6/27  2   36.00 × 10 - 1                                                                    2.56                                                                              28.00 × 10 - 1                                                                   2.45                                                                              2.45/0.079                                         26.00 × 10 - 1                                                                    2.41                                                                              24.00 × 10 - 1*                                                                  2.38                                         6/28  3   41.00 × 10 - 1                                                                    2.61                                                                              56.00 × 10 - 1                                                                   2.75                                                                              2.73/0.080                                         57.00 × 10 - 1                                                                    2.76                                                                              61.00 × 10 - 1                                                                   2.79                                         7/3   8   10.70 × 10 - 3                                                                    4.03                                                                              6.60 × 10 - 3                                                                    3.82                                                                              3.98/0.107                                         11.50 × 10 - 3                                                                    4.06                                                                              9.80 × 10 - 3                                                                    3.99                                         7/8   13  9.40 × 10 - 4                                                                     4.97                                                                              11.70 × 10 - 4                                                                   5.07                                                                              5.03/0.095                                         8.50 × 10 - 4                                                                     4.93                                                                              13.90 × 10 - 4                                                                   5.14                                         7/11  16   2.91 × 10 - 5@                                                                   5.46                                                                              2.38 × 10 - 5                                                                    5.38                                                                              5.39/0.096                                         1.90 × 10 - 5                                                                     5.28                                                                              2.40 × 10 - 5                                                                    5.38                                                    2.00 × 10 - 5*                                                                   5.30                                                                              3.30 × 10 - 5                                                                    5.52                                                    2.00 × 10 - 5*                                                                   5.30                                                                              3.20 × 10 - 5                                                                    5.51                                         7/19  24  5.80 × 10 - 5                                                                     5.76                                                                              4.80 × 10 - 5                                                                    5.68                                                                              5.74/0.040                                         5.50 × 10 - 5                                                                     5.74                                                                              5.90 × 10 - 5                                                                    5.77                                         __________________________________________________________________________     #The plate was either too smeared to count or too contaminated with mold      to count.                                                                     *The actual total colony count on a plate was less than 25 and is             therefore considered an estimate.                                             @The actual total colony count on a plate was greater than 250 and is         therefore considered an estimate.                                        

                                      TABLE III                                   __________________________________________________________________________    THE EFFECT OF PURE LIMONENE ON MICROBIAL COUNTS                               RUN NUMBER 2      INCUBATION TEMPERATURE 40 DEGREES F.                        OIL LEVEL .003    DATE PUT INTO STORAGE 6/25/91                                     TIME                                                                              SAMPLE       DUPLICATE    AVE. +/- SD                               DATE  IN  COUNTS       COUNTS       LOG                                       PLATED                                                                              DAYS                                                                              OSA      LOG OSA      LOG CFU                                       __________________________________________________________________________    6/25  0   31.00 × 10 - 1                                                                   2.49                                                                              25.00 × 10 - 1                                                                   2.40                                                                              2.45/0.064                                6/26  1   27.00 × 10 - 1                                                                   2.43                                                                              14.00 × 10 - 1*                                                                  2.15                                                                              2.37/0.150                                          25.00 × 10 - 1                                                                   2.40                                                                              31.00 × 10 - 1                                                                   2.49                                          6/27  2   38.00 × 10 - 1                                                                   2.58                                                                              29.00 × 10 - 1                                                                   2.46                                                                              2.41/0.137                                          21.00 × 10 - 1*                                                                  2.32                                                                              19.00 × 10 - 1*                                                                  2.28                                          6/28  3   45.00 × 10 - 1                                                                   2.65                                                                              66.00 × 10 - 1                                                                   2.82                                                                              2.73/0.090                                          62.00 × 10 -  1                                                                  2.79                                                                              45.00 × 10 - 1                                                                   2.65                                          7/3   8   6.10 × 10 - 3                                                                    3.79                                                                              4.30 × 10 - 3                                                                    3.63                                                                              3.73/0.117                                          7.40 × 10 - 3                                                                    3.87                                                                              4.40 × 10 - 3                                                                    3.64                                          7/8   13  4.50 × 10 - 4                                                                    4.65                                                                              #            4.71/0.041                                          5.60 × 10 - 4                                                                    4.75                                                                              #                                                                5.15 × 10 - 4                                                                    4.71                                                                              #                                                                5.18 × 10 - 4                                                                    4.71                                                                              #                                                      7/11  16  2.12 × 10 - 5                                                                    5.33                                                                              1.72 × 10 - 5                                                                    5.24                                                                              5.31/0.056                                          2.11 × 10 - 5                                                                    5.32                                                                              1.64 × 10 - 5                                                                    5.21                                                     2.20 × 10 - 5*                                                                  5.34                                                                               2.20 × 10 - 5*                                                                  5.34                                                     2.40 × 10 - 5*                                                                  5.38                                                                               2.00 × 10 - 5*                                                                  5.30                                          7/19  24  5.30 × 10 - 5                                                                    5.72                                                                              4.00 × 10 - 5                                                                    5.60                                                                              5.68/0.055                                          4.90 × 10 - 5                                                                    5.69                                                                              5.10 × 10 - 5                                                                    5.71                                          __________________________________________________________________________     #The plate was either too smeared to count or too contaminated with mold      to count.                                                                     *The actual total colony count on a plate was less than 25 and is             therefore considered an estimate.                                             @The actual total colony count on a plate was greater than 250 and is         therefore considered an estimate                                         

                                      TABLE III                                   __________________________________________________________________________    THE EFFECT OF PURE LIMONENE ON MICROBIAL COUNTS                               RUN NUMBER 2         INCUBATION TEMPERATURE 40 DEGREES F.                     OIL LEVEL .008       DATE PUT INTO STORAGE 6/25/91                                  TIME                                                                              SAMPLE         DUPLICATE     AVE. +/- SD                            DATE  IN  COUNTS         COUNTS        LOG                                    PLATED                                                                              DAYS                                                                              OSA        LOG OSA       LOG CFU                                    __________________________________________________________________________    6/25  0   24.00 × 10 - 1*                                                                    2.38                                                                              #             2.38                                   6/26  1   22.00 × 10 - 1*                                                                    2.34                                                                              22.00 × 10 - 1*                                                                   2.48                                                                              2.34/0.033                                       20.00 × 10 - 1*                                                                    2.30                                                                              24.00 × 10 - 1*                                                                   2.38                                       6/27  2   29.00 × 10 - 1                                                                     2.46                                                                              30.00 × 10 - 1                                                                    2.48                                                                              2.39/0.096                                       19.00 × 10 - 1*                                                                    2.28                                                                              22.00 × 10 - 1*                                                                   2.34                                       6/28  3   73.00 × 10 - 1                                                                     2.86                                                                              48.00 × 10 - 1                                                                    2.68                                                                              2.62/0.193                                       29.00 × 10 - 1                                                                     2.46                                                                              29.00 × 10 - 1                                                                    2.46                                       7/3   8    2.64 × 10 - 3@                                                                    3.42                                                                              1.85 × 10 - 3                                                                     3.27                                                                              3.27/0.106                                       2.44 × 10 - 3                                                                      3.39                                                                              1.51 × 10 - 3                                                                     3.18                                                  1.80 × 10 - 3*                                                                    3.26                                                                               1.40 × 10 - 3*                                                                   3.15                                                  2.20 × 10 - 3*                                                                    3.34                                                                               1.40 × 10 - 3*                                                                   3.15                                       7/8   13  0.92 × 10 - 4                                                                      3.96                                                                              1.40 × 10 - 4                                                                     4.15                                                                              4.06/0.145                                       0.82 × 10 - 4                                                                      3.91                                                                              1.63 × 10 - 4                                                                     4.21                                       7/11  16  1.53 × 10 - 4                                                                      4.18                                                                               4.14 × 10 - 4@                                                                   4.62                                                                              4.41/0.211                                       1.85 × 10 - 4                                                                      4.27                                                                               3.25 × 10 - 4@                                                                   4.51                                                  1.50 × 10 - 4*                                                                    4.18                                                                              4.70 × 10 - 4                                                                     4.67                                                  1.70 × 10 - 4*                                                                    4.23                                                                              3.90 × 10 - 4                                                                     4.59                                       7/19  24  1.67 × 10 - 5                                                                      5.22                                                                              1.17 × 10 - 5                                                                     5.07                                                                              5.15/0.090                                       1.75 × 10 - 5                                                                      5.24                                                                              1.19 × 10 - 5                                                                     5.08                                       __________________________________________________________________________     #The plate was either too smeared to count or too contaminated with mold      to count.                                                                     *The actual total colony count on a plate was less than 25 and is             therefore considered an estimate.                                             @The actual total colony count on a plate was greater than 250 and is         therefore considered an estimate.                                        

                                      TABLE III                                   __________________________________________________________________________    THE EFFECT OF PURE LIMONENE ON MICROBIAL COUNTS                               RUN NUMBER 2      INCUBATION TEMPERATURE 40 DEGREES F.                        OIL LEVEL .0158   DATE PUT INTO STORAGE 6/25/91                                     TIME                                                                              SAMPLE       DUPLICATE    AVE. +/- SD                               DATE  IN  COUNTS       COUNTS       LOG                                       PLATED                                                                              DAYS                                                                              OSA      LOG OSA      LOG CFU                                       __________________________________________________________________________    6/25  0   17.00 × 10 - 1*                                                                  2.23                                                                              14.00 × 10 - 1*                                                                  2.15                                                                              2.19/0.057                                6/26  1   29.00 × 10 - 1                                                                   2.46                                                                              16.00 × 10 - 1*                                                                  2.04                                                                              2.17/0.274                                          21.00 × 10 - 1*                                                                  2.32                                                                               7.00 × 10 - 1*                                                                  1.85                                          6/27  2   20.00 × 10 - 1*                                                                  2.30                                                                              19.00 × 10 - 1*                                                                  2.28                                                                              2.35/0.067                                          25.00 × 10 - 1                                                                   2.40                                                                              26.00 × 10 - 1                                                                   2.41                                          6/28  3   27.00 × 10 - 1                                                                   2.43                                                                              45.00 × 10 - 1                                                                   2.65                                                                              2.48/0.130                                          22.00 × 10 - 1*                                                                  2.34                                                                              31.00 × 10 - 1                                                                   2.49                                          7/3   8   0.51 × 10 - 3                                                                    2.71                                                                              0.32 × 10 - 3                                                                    2.51                                                                              2.60/0.083                                          0.39 × 10 - 3                                                                    2.59                                                                              0.38 × 10 - 3                                                                    2.58                                          7/8   13  1.48 × 10 - 3                                                                    3.17                                                                              1.03 × 10 - 3                                                                    3.01                                                                              3.15/0.100                                          1.79 × 10 - 3                                                                    3.25                                                                              1.42 × 10 - 3                                                                    3.15                                          7/11  16  6.20 × 10 - 2                                                                    2.79                                                                              11.30 × 10 - 2                                                                   3.05                                                                              2.91/0.172                                          5.40 × 10 - 2                                                                    2.73                                                                              11.40 × 10 - 2                                                                   3.06                                          7/19  24  1.62 × 10 - 3                                                                    3.21                                                                              1.67 × 10 - 3                                                                    3.22                                                                              3.23/0.018                                          1.72 × 10 - 3                                                                    3.24                                                                              1.76 × 10 - 3                                                                    3.25                                          __________________________________________________________________________     #The plate was either too smeared to count or too contaminated with mold      to count.                                                                     *The actual total colony count on a plate was less than 25 and is             therefore considered an estimate.                                             @The actual total colony count on a plate was more than 250 and is            therefore considered an estimate.                                        

                                      TABLE III                                   __________________________________________________________________________    THE EFFECT OF PURE LIMONENE ON MICROBIAL COUNTS                               RUN NUMBER 2      INCUBATION TEMPERATURE 40 DEGREES F.                        OIL LEVEL .018    DATE PUT INTO STORAGE 6/25/91                                     TIME                                                                              SAMPLE       DUPLICATE    AVE. +/- SD                               DATE  IN  COUNTS       COUNTS       LOG                                       PLATED                                                                              DAYS                                                                              OSA      LOG OSA      LOG CFU                                       __________________________________________________________________________    6/25  0   26.00 × 10 - 1                                                                   2.42                                                                              18.00 × 10 - 1*                                                                  2.26                                                                              2.34/0.113                                6/26  1   20.00 × 10 - 1*                                                                  2.30                                                                              17.00 × 10 - 1*                                                                  2.23                                                                              2.31/0.064                                          24.00 × 10 - 1*                                                                  2.38                                                                              22.00 × 10 - 1*                                                                  2.34                                          6/27  2   16.00 × 10 - 1*                                                                  2.20                                                                              24.00 × 10 - 1*                                                                  2.38                                                                              2.37/0.135                                          23.00 × 10 - 1*                                                                  2.36                                                                              34.00 × 10 - 1                                                                   2.53                                          6/28  3   18.00 × 10 - 1*                                                                  2.26                                                                              18.00 × 10 - 1*                                                                  2.26                                                                              2.24/0.096                                          13.00 × 10 - 1*                                                                  2.11                                                                              22.00 × 10 -  1*                                                                 2.34                                          7/3   8    0.22 × 10 - 3*                                                                  2.34                                                                               0.21 × 10 - 3*                                                                  2.32                                                                              2.36/0.040                                          0.26 × 10 - 3                                                                    2.41                                                                               0.24 × 10 - 3*                                                                  2.38                                          7/8   13  0.47 × 10 - 3                                                                    2.67                                                                              0.98 × 10 - 3                                                                    2.99                                                                              2.84/0.156                                          0.55 × 10 - 3                                                                    2.74                                                                              0.89 × 10 - 3                                                                    2.95                                          7/11  16  5.50 × 10 - 2                                                                    2.74                                                                              5.10 × 10 - 2                                                                    2.71                                                                              2.67/0.072                                          3.80 × 10 - 2                                                                    2.58                                                                              4.40 × 10 - 2                                                                    2.64                                          7/19  24  6.90 × 10 - 2                                                                    2.84                                                                              12.60 × 10 - 2                                                                   3.10                                                                              2.93/0.117                                          6.80 × 10 - 2                                                                    2.83                                                                              9.40 × 10 - 2                                                                    2.97                                                    6.70 × 10 - 2                                                                    2.83                                                                              10.60 × 10 - 2                                                                   3.03                                          __________________________________________________________________________     #The plate was either too smeared to count or too contaminated with mold      to count.                                                                     *The actual total colony count on a plate was less than 25 and is             therefore considered an estimate.                                             @The actual total colony count on a plate was more than 250 and is            therefore considered an estimate.                                        

                                      TABLE III                                   __________________________________________________________________________    THE EFFECT OF PURE LIMONENE ON MICROBIAL COUNTS                               RUN NUMBER 2      INCUBATION TEMPERATURE 40 DEGREES F.                        OIL LEVEL .033    DATE PUT INTO STORAGE 6/25/91                                     TIME                                                                              SAMPLE       DUPLICATE    AVE. +/- SD                               DATE  IN  COUNTS       COUNTS       LOG                                       PLATED                                                                              DAYS                                                                              OSA      LOG OSA      LOG CFU                                       __________________________________________________________________________    6/25  0   17.00 × 10 - 1*                                                                  2.23                                                                              22.00 × 10 - 1*                                                                  2.34                                                                              2.29/0.778                                6/26  1    9.00 × 10 - 1*                                                                  1.95                                                                              20.00 × 10 - 1*                                                                  2.30                                                                              2.17/0.156                                          18.00 × 10 - 1*                                                                  2.26                                                                              15.00 × 10 - 1*                                                                  2.18                                          6/27  2   12.00 × 10 - 1*                                                                  2.08                                                                              15.00 × 10 - 1*                                                                  2.18                                                                              2.15/0.047                                          15.00 × 10 - 1*                                                                  2.18                                                                              14.00 × 10 - 1*                                                                  2.15                                          6/28  3   22.00 × 10 - 1*                                                                  2.34                                                                              14.00 × 10 - 1*                                                                  2.15                                                                              2.16/0.161                                          16.00 × 10 - 1*                                                                  2.20                                                                               9.00 × 10 -  1*                                                                 1.95                                          7/3   8    0.09 × 10 - 3*                                                                  1.95                                                                               0.13 × 10 - 3*                                                                  2.11                                                                              2.09/0.146                                           0.10 × 10 - 3*                                                                  2.00                                                                              0.19 × 10 - 3                                                                    2.28                                          7/8   13   0.20 × 10 - 3*                                                                  2.30                                                                               0.18 × 10 - 3*                                                                  2.26                                                                              2.31/0.071                                           0.18 × 10 - 3*                                                                  2.26                                                                              0.26 × 10 - 3                                                                    2.41                                          7/11  16  #             1.40 × 10 - 2*                                                                  2.15                                                                              2.23/0.106                                          #             2.00 × 10 - 2*                                                                  2.30                                          7/19  24  10.00 × 10 - 1*                                                                  2.00                                                                               8.00 × 10 - 1*                                                                  1.90                                                                              1.99/0.090                                          11.00 × 10 - 1*                                                                  2.04                                                                               7.00 × 10 - 1*                                                                  1.85                                                    12.00 × 10 - 1*                                                                  2.08                                                                              11.00 × 10 - 1*                                                                  2.04                                          __________________________________________________________________________     #The plate was either too smeared to count or too contaminated with mold      to count.                                                                     *The actual total colony count on a plate was less than 25 and is             therefore considered an estimate.                                             @The actual total colony count on a plate was more than 250 and is            therefore considered an estimate.                                        

                                      TABLE IV                                    __________________________________________________________________________    THE EFFECT OF PURE LIMONENE ON MICROBIAL COUNTS                               RUN NUMBER 2        INCUBATION TEMPERATURE 40 DEGREES F.                      OIL LEVEL .001 (CONTROL)                                                                          DATE PUT INTO STORAGE 6/25/91                                   TIME                                                                              SAMPLE        DUPLICATE     AVE. +/- SD                             DATE  IN  COUNTS        COUNTS        LOG                                     PLATED                                                                              DAYS                                                                              APDA      LOG APDA      LOG CFU                                     __________________________________________________________________________    6/25  0   13.00 × 10 - 1*                                                                   2.11                                                                               7.00 × 10 - 1*                                                                   1.85                                                                              1.98/0.184                              6/26  1   15.00 × 10 - 1*                                                                   2.18                                                                              15.00 × 10 - 1*                                                                   2.18                                                                              2.14/0.067                                        11.00 × 10 - 1*                                                                   2.04                                                                              14.00 × 10 - 1*                                                                   2.15                                        6/27  2   35.00 × 10 - 1                                                                    2.54                                                                              24.00 × 10 - 1*                                                                   2.38                                                                              2.41/0.089                                        22.00 × 10 - 1*                                                                   2.34                                                                              24.00 × 10 - 1*                                                                   2.38                                        6/28  3   45.00 × 10 - 1                                                                    2.65                                                                              40.00 × 10 - 1                                                                    2.60                                                                              2.66/0.049                                        53.00 × 10 - 1                                                                    2.72                                                                              46.00 × 10 - 1                                                                    2.66                                        7/3   8   11.00 × 10 - 3                                                                    4.04                                                                              7.80 × 10 - 3                                                                     3.89                                                                              3.98/0.081                                        11.40 × 10 - 3                                                                    4.06                                                                              8.80 × 10 - 3                                                                     3.94                                        7/8   13   8.65 × 10 - 4@                                                                   4.94                                                                              #             4.96/0.044                                         8.16 × 10 - 4@                                                                   4.91                                                                              #                                                               10.20 × 10 - 4                                                                    5.01                                                                              #                                                               9.50 × 10 - 4                                                                     4.98                                                                              #                                                     7/11  16  2.11 × 10 - 5                                                                     5.32                                                                               2.86 × 10 - 5@                                                                   5.46                                                                              5.37/0.047                                        2.15 × 10 - 5                                                                     5.33                                                                              2.40 × 10 - 5                                                                     5.38                                                  2.50 × 10 - 5                                                                     5.40                                                                              #                                                                2.30 × 10 - 5*                                                                   5.36                                                                               2.30 × 10 - 5*                                                                   5.36                                        7/19  24  6.40 × 10 - 5                                                                     5.81                                                                              5.50 × 10 - 5                                                                     5.74                                                                              5.79/0.033                                        6.00 × 10 - 5                                                                     5.78                                                                              6.50 × 10 - 5                                                                     5.81                                        __________________________________________________________________________     #The plate was either too smeared to count or too contaminated with mold      to count.                                                                     *The actual total colony count on a plate was less than 25 and is             therefore considered an estimate.                                             @The actual total colony count on a plate was more than 250 and is            therefore considered an estimate.                                        

                                      TABLE IV                                    __________________________________________________________________________    THE EFFECT PURE LIMONENE ON MICROBIAL COUNTS                                  RUN NUMBER 2        INCUBATION TEMPERATURE 40 DEGREES F.                      OIL LEVEL .003      DATE PUT INTO STORAGE 6/25/91                                   TIME                                                                              SAMPLE        DUPLICATE     AVE. +/- SD                             DATE  IN  COUNTS        COUNTS        LOG                                     PLATED                                                                              DAYS                                                                              APDA      LOG APDA      LOG CFU                                     __________________________________________________________________________    6/25  0    8.00 × 10 - 1*                                                                   1.90                                                                              12.00 × 10 - 1*                                                                   2.08                                                                              1.99/0.127                              6/26  1   17.00 × 10 - 1*                                                                   2.23                                                                              13.00 × 10 - 1*                                                                   2.11                                                                              2.18/0.079                                        18.00 × 10 - 1*                                                                   2.26                                                                              13.00 × 10 - 1*                                                                   2.11                                        6/27  2   24.00 × 10 - 1*                                                                   2.38                                                                              20.00 × 10 - 1*                                                                   2.30                                                                              2.30/0.086                                        22.00 × 10 - 1*                                                                   2.34                                                                              15.00 × 10 - 1*                                                                   2.18                                        6/28  3   39.00 × 10 - 1                                                                    2.59                                                                              40.00 × 10 - 1                                                                    2.60                                                                              2.60/0.013                                        38.00 × 10 - 1                                                                    2.58                                                                              41.00 × 10 - 1                                                                    2.61                                        7/5   8   5.00 × 10 - 3                                                                     3.70                                                                              3.20 × 10 - 3                                                                     3.51                                                                              3.68/0.126                                        8.30 × 10 - 3                                                                     3.92                                                                              4.00 × 10 - 3                                                                     3.60                                                   5.58 × 10 - 3@                                                                   3.75                                                                               4.06 × 10 - 3@                                                                   3.61                                                   5.50 × 10 - 3@                                                                   3.74                                                                               4.18 × 10 - 3@                                                                   3.62                                        7/8   13  5.80 × 10 - 4                                                                     4.76                                                                              #             4.72/0.048                                        4.50 × 10 - 4                                                                     4.65                                                                              #                                                                5.30 × 10 - 4@                                                                   4.72                                                                              #                                                                5.49 × 10 - 4@                                                                   4.74                                                                              #                                                     7/11  16   5.49 × 10 - 5@                                                                   5.74                                                                              1.76 × 10 - 5                                                                     5.25                                                                              5.48/0.250                                        4.90 × 10 - 5                                                                     5.69                                                                              1.74 × 10 - 5                                                                     5.24                                                  6.10 × 10 - 5                                                                     5.79                                                                               2.10 × 10 -  5*                                                                  5.32                                                                 2.00 × 10 - 5*                                                                   5.30                                        7/19  24  3.80 × 10 - 5                                                                     5.58                                                                              4.60 × 10 - 5                                                                     5.66                                                                              5.64/0.068                                        4.00 × 10 - 5                                                                     5.60                                                                              5.40 × 10 - 5                                                                     5.73                                        __________________________________________________________________________     #The plate was either too smeared to count or too contaminated with mold      to count.                                                                     *The actual total colony count on a plate was less than 25 and is             therefore considered an estimate.                                             @The actual total colony count on a plate was more than 250 and is            therefore considered an estimate.                                        

                                      TABLE IV                                    __________________________________________________________________________    THE EFFECT OF PURE LIMONENE ON MICROBIAL COUNTS                               RUN NUMBER 2      INCUBATION TEMPERATURE 40 DEGREES F.                        OIL LEVEL .008    DATE PUT INTO STORAGE 6/25/91                                     TIME                                                                              SAMPLE       DUPLICATE    AVE. +/- SD                               DATE  IN  COUNTS       COUNTS       LOG                                       PLATED                                                                              DAYS                                                                              APDA     LOG APDA     LOG CFU                                       __________________________________________________________________________    6/25  0    8.00 × 10 - 1*                                                                  1.90                                                                               6.00 × 10 - 1*                                                                  1.78                                                                              1.86/0.069                                                        8.00 × 10 - 1*                                                                  1.90                                          6/26  1    8.00 × 10 - 1*                                                                  1.90                                                                              10.00 × 10 - 1*                                                                  2.00                                                                              1.94/0.130                                          12.00 × 10 - 1*                                                                  2.08                                                                               6.00 × 10 - 1*                                                                  1.78                                          6/27  2   13.00 × 10 - 1*                                                                  2.11                                                                              22.00 × 10 - 1*                                                                  2.34                                                                              2.23/0.139                                          23.00 × 10 - 1*                                                                  2.36                                                                              13.00 × 10 - 1*                                                                  2.11                                          6/28  3   23.00 × 10 - 1*                                                                  2.36                                                                              25.00 × 10 - 1                                                                   2.40                                                                              2.37/0.025                                          22.00 × 10 - 1*                                                                  2.34                                                                              23.00 × 10 - 1*                                                                  2.36                                          7/3   8   2.23 × 10 - 3                                                                    3.35                                                                              1.76 × 10 - 3                                                                    3.25                                                                              3.28/0.144                                          2.20 × 10 - 3                                                                    3.34                                                                              1.53 × 10 - 3                                                                    3.18                                                    2.60 × 10 - 3                                                                    3.41                                                                              3.20 × 10 - 3                                                                    3.51                                                     1.20 × 10 - 3*                                                                  3.08                                                                               1.40 × 10 - 3*                                                                  3.15                                          7/8   13  1.00 × 10 - 4                                                                    4.00                                                                              1.56 × 10 - 4                                                                    4.19                                                                              4.09/0.132                                          0.90 × 10 - 4                                                                    3.95                                                                              1.64 × 10 - 4                                                                    4.21                                          7/11  16  1.73 × 10 - 4                                                                    4.24                                                                              86.00 × 10 - 4                                                                   5.93                                                                              5.09/0.956                                          1.97 × 19 - 4                                                                    4.29                                                                              82.00 × 10 - 4                                                                   5.91                                          7/19  24  1.44 × 10 - 5                                                                    5.16                                                                              1.68 × 10 - 5                                                                    5.23                                                                              5.20/0.034                                          1.71 × 10 - 5                                                                    5.23                                                                              1.55 × 10 - 5                                                                    5.19                                          __________________________________________________________________________     #The plate was either too smeared to count or too contaminated by mold to     count.                                                                        *The actual total colony count on a plate was less than 25 and is             therefore considered an estimate.                                             @The actual total colony count on a plate was greater than 250 and is         therefore considered an estimate.                                        

                                      TABLE IV                                    __________________________________________________________________________    THE EFFECT OF PURE LIMONENE ON MICROBIAL COUNTS                               RUN NUMBER 2      INCUBATION TEMPERATURE 40 DEGREES F.                        OIL LEVEL .0158   DATE PUT INTO STORAGE 6/25/91                                     TIME                                                                              SAMPLE       DUPLICATE    AVE. +/- SD                               DATE  IN  COUNTS       COUNTS       LOG                                       PLATED                                                                              DAYS                                                                              APDA     LOG APDA     LOG CFU                                       __________________________________________________________________________    6/25  0    5.00 × 10 - 1*                                                                  1.70                                                                              10.00 × 10 - 1*                                                                  2.00                                                                              1.87/0.153                                           8.00 × 10 - 1*                                                                  1.90                                                       6/26  1   17.00 × 10 - 1*                                                                  2.23                                                                              13.00 × 10 - 1*                                                                  2.11                                                                              2.12/0.082                                          12.00 × 10 - 1*                                                                  2.08                                                                              11.00 × 10 - 1*                                                                  2.04                                          6/27  2    8.00 × 10 - 1*                                                                  1.90                                                                               9.00 × 10 - 1*                                                                  1.95                                                                              1.95/0.099                                           7.00 × 10 - 1*                                                                  1.85                                                                              12.00 × 10 - 1*                                                                  2.08                                          6/28  3   15.00 × 10 - 1*                                                                  2.18                                                                              16.00 × 10 - 1*                                                                  2.20                                                                              2.16/0.077                                          16.00 × 10 - 1*                                                                  2.20                                                                              11.00 × 10 - 1*                                                                  2.04                                          7/3   8   0.46 × 10 - 3                                                                    2.66                                                                               0.20 × 10 - 3*                                                                  2.30                                                                              2.54/0.183                                          0.50 × 10 - 3                                                                    2.70                                                                              0.31 × 10 - 3                                                                    2.49                                          7/8   13  1.13 × 10 - 3                                                                    3.05                                                                              0.97 × 10 - 3                                                                    2.99                                                                              3.04/0.104                                          1.50 × 10 - 3                                                                    3.18                                                                              0.87 × 10 - 3                                                                    2.94                                          7/11  16  5.30 × 10 - 2                                                                    2.72                                                                              8.70 × 10 - 2                                                                    2.94                                                                              2.85/0.154                                          5.20 × 10 - 2                                                                    2.72                                                                              10.40 × 10 - 2                                                                   3.02                                          7/19  24  1.25 × 10 - 3                                                                    3.10                                                                              1.10 × 10 - 3                                                                    3.04                                                                              3.09/0.039                                          1.36 × 10 - 3                                                                    3.13                                                                              1.17 × 10 - 3                                                                    3.07                                          __________________________________________________________________________     #The plate was either too smeared to count or too contaminated by mold to     count.                                                                        *The actual total colony count on a plate was less than 25 and is             therefore considered an estimate.                                             @The actual total colony count on a plate was greater than 250 and is         therefore considered an estimate.                                        

                                      TABLE IV                                    __________________________________________________________________________    THE EFFECT OF PURE LIMONENE ON MICROBIAL COUNTS                               RUN NUMBER 2      INCUBATION TEMPERATURE 40 DEGREES F.                        OIL LEVEL .018    DATE PUT INTO STORAGE 6/25/91                                     TIME                                                                              SAMPLE       DUPLICATE    AVE. +/- SD                               DATE  IN  COUNTS       COUNTS       LOG                                       PLATED                                                                              DAYS                                                                              APDA     LOG APDA     LOG CFU                                       __________________________________________________________________________    6/25  0   11.00 × 10 - 1*                                                                  2.04                                                                              12.00 × 10 - 1*                                                                  2.08                                                                              1.98/0.134                                          10.00 × 10 - 1*                                                                  2.00                                                                               6.00 × 10 - 1*                                                                  1.78                                          6/26  1   13.00 × 10 - 1*                                                                  2.11                                                                               8.00 × 10 - 1*                                                                  1.90                                                                              2.06/0.120                                          15.00 × 10 - 1*                                                                  2.18                                                                              11.00 × 10 - 1*                                                                  2.04                                          6/27  2   13.00 × 10 - 1*                                                                  2.11                                                                              14.00 × 10 - 1*                                                                  2.15                                                                              2.14/0.092                                          11.00 × 10 - 1*                                                                  2.04                                                                              18.00 × 10 - 1*                                                                  2.26                                          6/28  3   14.00 × 10-*                                                                     2.15                                                                              10.00 × 10 -  1*                                                                 2.00                                                                              2.10/0.127                                          10.00 × 10 - 1*                                                                  2.00                                                                              18.00 × 10 - 1*                                                                  2.26                                          7/3   8   0.33 × 10 - 3                                                                    2.52                                                                              0.25 × 10 - 3                                                                    2.40                                                                              2.38/0.110                                           0.22 × 10 - 3*                                                                  2.34                                                                               0.18 × 10 - 3*                                                                  2.26                                          7/8   13  0.55 × 10 - 3                                                                    2.74                                                                              #            2.76/0.028                                          0.60 × 10 - 3                                                                    2.78                                                                              #                                                      7/11  16  3.90 × 10 - 2                                                                    2.59                                                                              4.20 × 10 - 2                                                                    2.62                                                                              2.58/0.035                                          3.60 × 10 - 2                                                                    2.56                                                                              3.50 × 10 - 2                                                                    2.54                                          7/19  24  5.20 × 10 - 2                                                                    2.72                                                                              5.20 × 10 - 2                                                                    2.72                                                                              2.68/0.062                                          4.20 × 10 - 2                                                                    2.62                                                                              4.10 × 10 - 2                                                                    2.61                                                    4.50 × 10 - 2                                                                    2.65                                                                              5.70 × 10 - 2                                                                    2.76                                          __________________________________________________________________________     #The plate was either too smeared to count or too contaminated by mold to     count.                                                                        *The actual total colony count on a plate was less than 25 and is             therefore considered an estimate.                                             @The actual total colony count on a plate was greater than 250 and is         therefore considered an estimate.                                        

                                      TABLE IV                                    __________________________________________________________________________    THE EFFECT OF PURE LIMONENE ON MICROBIAL COUNTS                               RUN NUMBER 2      INCUBATION TEMPERATURE 40 DEGREES F.                        OIL LEVEL .033    DATE PUT INTO STORAGE 6/25/91                                     TIME                                                                              SAMPLE       DUPLICATE    AVE. +/- SD                               DATE  IN  COUNTS       COUNTS       LOG                                       PLATED                                                                              DAYS                                                                              APDA     LOG APDA     LOG CFU                                       __________________________________________________________________________    6/25  0   18.00 × 10 - 1*                                                                  2.26                                                                              5.00 × 10 - 1*                                                                   1.70                                                                              1.89/0.300                                          4.00 × 10 - 1*                                                                   1.60                                                                              10.00 × 10 - 1*                                                                  2.00                                          6/26  1   11.00 × 10 - 1*                                                                  2.04                                                                              4.00 × 10 - 1*                                                                   1.60                                                                              1.85/0.184                                          8.00 × 10 - 1*                                                                   1.90                                                                              7.00 × 10 - 1*                                                                   1.85                                          6/27  2   9.00 × 10 - 1*                                                                   1.95                                                                              12.00 × 10 - 1*                                                                  2.08                                                                              1.97/0.077                                          9.00 × 10 - 1*                                                                   1.95                                                                              8.00 × 10 - 1*                                                                   1.90                                          6/28  3   14.00 × 10 - 1*                                                                  2.15                                                                              18.00 ×  10 - 1*                                                                 2.26                                                                              2.12/0.110                                          10.00 × 10 - 1*                                                                  2.00                                                                              12.00 × 10 - 1*                                                                  2.08                                          7/3   8   0.10 × 10 - 3*                                                                   2.00                                                                              0.09 × 10 - 3*                                                                   1.95                                                                              1.91/0.075                                          0.07 × 10 - 3*                                                                   1.85                                                                              0.07 × 10 - 3*                                                                   1.85                                          7/8   13  0.04 × 10 - 3*                                                                   1.60                                                                              0.46 × 10 - 3                                                                    2.66                                                                              2.21/0.446                                          0.17 × 10 - 3*                                                                   2.23                                                                              0.23 × 10 - 3*                                                                   2.36                                          7/11  16  #            1.20 × 10 - 2*                                                                   2.08                                                                              2.10/0.021                                          #            1.30 × 10 - 2*                                                                   2.11                                          7/19  24  8.00 × 10 - 1*                                                                   1.90                                                                              1.00 × 10 - 1*                                                                   1.00                                                                              1.60/0.367                                          6.00 × 10 - 1*                                                                   1.78                                                                              2.00 × 10 - 1*                                                                   1.30                                                    8.00 × 10 - 1*                                                                   1.90                                                                              5.00 × 10 - 1*                                                                   1.70                                          __________________________________________________________________________     #The plate was either too smeared to count or too contaminated by mold to     count.                                                                        *The actual total colony count on a plate was less than 25 and is             therefore considered an estimate.                                             @The actual total colony count on a plate was greater than 250 and is         therefore considered an estimate.                                        

The University of Florida's Citrus Research Center conducted fourexperiments on juices in containers with and without flavor barriers todetermine if a high D-limonene count inhibits microbial numbers. Theconclusion reached based on the following test results is that all ofthe oxygen barrier materials listed above, namely, EVOH, polyamide(nylon) and PET, prevent D-limonene absorption and migration.

The first experiment tested the hypothesis that peel oil inhibitsmicrobial number. The procedure followed was: juice homogenized to 72.3degree Brix (by refractometer) pumpout was made to 0, 0.005, 0.015,0.025, 0.035 and 0.045% oil. The samples were diluted back to 11.8%Brix, and 5 mL was pipetted into each of twenty 10 mL test tubes withTeflon screw caps. The tubes were held at 4 degrees C, and sampled at 0,1, 3, 6, 9, 13, 17, 20, 28, 38, 50 days for microbial counts on OSA andADPA plates. After two days the experiment was aborted due to the lackof viable microorganisms in the tubes to seed the process.

The second experiment repeated the first experiment 1, but with a fewminor exceptions. Each essence addition level was spiked with 10 mLunpasteurized, fresh squeezed, homogenized, juice that had been held 4days at refrigerator temperatures and 1 day (the final day) at roomtemperature. This was to seed the juice to make certain microorganismswere present. The proportions of juice and water were also different. 33g of concentrate (75 Brix--the same stock used above) received 0.,0.005, 0.015, 0.025, 0.035, or 0.045% additions of peel oil. 160 mL ofdistilled water were added along with the 10 mL of the juice. Contraryto the previous procedure, oils were run during and directly afteressence addition. The three highest values were very similar in Scottoil value. They were also similar in microbial growth. All three levelsinhibited microbial growth relative to the control. By the end of thethirty-eight day study, there were approximately 16 times as manyorganisms in the untreated sample as in the higher D-limonene samples onthe ADPA media and 10 times as many organisms in the untreated sample asin the higher D-limonene samples on the OSA media.

The third experiment basically repeated the first two experiments, butwith several differences. In previous experiments, essence was addeddirectly to the 72 Brix (normal) citrus concentrate. In the thirdexperiment, concentrate was first diluted to 41.1 Bx. Essence was addedto this concentrate once gelled lumps were placed in solution. A secondmodification dealt with inoculum type. Experiment 1 did not use aninoculum. Experiment 2 inoculated with fresh juice stored forapproximately 3 days. In these experiments, the time required toinoculate all batches was spread out over a couple of hours.Pre-dilution to 41.1 Bx reduced inoculum addition to approximately 30minutes. A third modification was that D-limonene (not citrus essence)was used. Ultrapure D-limonene replaced the essence used in the firstand second experiments.

The following results were achieved: Limonene and Microorganisms:Previous runs had shown that some component of peel oil was a potentinhibitor of microorganism. This experiment showed that D-limonene wasat least one of the inhibiting species. Since D-limonene constitutes 95%of cold pressed peel oil, it is likely the major inhibitory entity injuice. The relationship between D-limonene concentration and microbialnumbers was overwhelmingly clear. There was over a 7000 fold differencein microorganisms in the 0% D-limonene sample as in the 0.033%D-limonene sample.

The fourth or last experiment proved that D-limonene has a markedinhibitory effect on citrus microorganisms. The purpose of thisexperiment was to determine whether D-limonene absorption by polymerscan translate into microbial differences.

The principal differences in procedure between this fourth experimentand the previous experiments were as follows:

1. 72 Brix concentrate was diluted to approximately 56 Bx.

2. 500 mL glass jars were sterilized. Sanitized samples of LDPE, PET,EVOH and Nylon were added to the bottles. A control bottle withoutpolymer was also sterilized.

3. Each D-limonene concentration (and the 0% D-limonene control) wereformulated in batches of 3000 mL. This required 672 g of 56 Brixconcentrate and 2464 mL of sterile distilled water. During the first(control) sample too much water was added. The final volume was 3254 mL,not 3136 mL. All other samples were formulated to 3254 g for the sake ofconsistency.

4. 99.5% pure D-limonene was added directly to the 56 Brix concentratewith an Eppendorf pipetter. D-limonene was dispersed by brisk agitationwith a large stainless steel spatula. The concentrate was stirredconstantly while water was being added. Mixing was in a nalgeen beaker.Target oil values were 0, 0.015, 0.025, 0.035 and 0.045.

5. 400 mL +/-2% of reconstituted juice were added to each 500 mL bottle.The bottles were immediately capped with foil lined screw caps. A 100 mLsample of each D-limonene percent was collected for oil and Brixdetermination.

6. All bottles were inoculated at the same time several hours later witha mixture consisting of freshly squeezed juice and peel washings.

The following results were achieved: Scalping and microbial numbers- Atthe 0.0008% D-limonene, there was no significant difference in microbialgrowth between the control (no polymer) and all the other juice samplescontaining polymers. This would be expected, since there was noD-limonene to scalp. There would be no scalping differences due toabsorption. As the amount of initial D-limonene increased, differencesin polymers became much more pronounced. Even at 0.0092% D-limonene,LDPE exhibited greater growth than the control and other polymers. Atthis level of D-limonene addition, there was not much separation betweenthe PET, EVOH, nylon and the control. At 0.011 and 0.0172% D-limonene,there were ample separations between the polymers. LDPE had the greatestmicrobial numbers (log CFU=>4) followed by PET (log CFU=3.9), with theblank control next at 3.8 CFU. EVOH was fourth at 3.57 (log CFU) withnylon showing the least growth at 3.44 (log CFU). This represents a 4.5fold difference between LDPE and nylon. Nylon was consistently thelowest in microbial numbers when there was enough of a difference to benoted. This experiment indicated that D-limonene absorption by the testpolymers can translate into microbial differencies.

Based on these tests, it was determined that a thin skin coat layer in alaminate that is impervious to D-limonene inhibits the microorganismsresponsible for spoilage in citrus beverages.

While the present invention has been illustrated and described asembodied in a barrier laminate for inhibiting the proliferation ofmicrobial growth and, thus, the migration of D-limonene from the citrusjuice in a carton, it is not intended to be limited to the detailsshown, since various modifications and structural changes may be madewithout departing in any way from the spirit of the present invention.

We claim:
 1. A method for extending the shelf life of a citrus juicestored in a paperboard carton formed from a laminate comprised of aplurality of layers having an innermost layer that contacts the juice,the method including the step of inhibiting the proliferation ofmicroorganisms in the juice by preventing an antimicrobial agent presentin the juice from migrating into the plurality of layers of the cartonby making the innermost layer of the carton impervious to theantimicrobial agent wherein said carton is formed from a barrierlaminate comprising:1) a paperboard substrate having an interior and anexterior surface, 2) a layer of heat sealable low density polyethylenecoated on said exterior surface of said paperboard substrate, 3) abarrier layer of nylon applied directly onto said interior surface ofsaid paperboard substrate, 4) a first tie layer of modified polyethyleneapplied directly on to said barrier layer of nylon, 5) a heat seal layerof low density polyethylene applied directly onto said first tie layerwherein the first tie layer adheres together the nylon barrier layer andthe low density polyethylene heat seat layer, 6) a second tie layerapplied directly onto said low density polyethylene heat seal layer saidsecond tie layer being a low density polyethylene based tie layer resin,and 7) a skin coat layer applied directly onto said second tie layersaid skin coat layer being a member selected from the group consistingof ethylene vinyl alcohol, polyethylene terephthalate and nylon, andwherein said second tie layer is modified low density polyethylene resinor modified polyethylene resin when the skin coat layer is either ethylvinyl alcohol or nylon, and wherein said second tie layer is modifiedlow density polyethylene resin when said skin coat layer is polyethyleneterephthalate.
 2. The method according to claim 1, wherein theantimicrobial agent is D-limonene.
 3. The method according to claim 1,wherein the innermost layer serves as a limited oxygen barrier.
 4. Themethod according to claim 3, wherein the limited oxygen barrier servesto maintain the loss of ascorbic acid in the juice.
 5. The methodaccording to claim 1, wherein the beverage is a citrus juice.
 6. Amethod for preserving the antimicrobial properties present in a citrusjuice stored in a paperboard carton formed from a laminate comprised ofa plurality of layers having an innermost layer that contacts the juice,the method including the step of preventing the antimicrobial agentD-limonene present in the juice from migrating into the plurality oflayers of the carton by making the innermost layer of the cartonimpervious to the antimicrobial agent D-limonene, wherein said carton isformed from a barrier laminate comprising:1) a paperboard substratehaving an interior and an exterior surface, 2) a layer of heat sealablelow density polyethylene coated on said exterior surface of saidpaperboard substrate. 3) a barrier layer of nylon applied directly ontosaid interior surface of said paperboard substrate, 4) a first tie layerof modified polyethylene applied directly on to said barrier layer ofnylon, 5) a heat seal layer of low density polyethylene applied directlyonto said first tie layer wherein the first tie layer adheres togetherthe nylon barrier layer and the low density polyethylene heat seallayer, 6) a second tie layer applied directly onto said low densitypolyethylene heat seal layer said second tie layer being a low densitypolyethylene based tie layer resin, and 7) a skin coat layer applieddirectly onto said second tie layer said skin coat layer being a memberselected from the group consisting of ethylene vinyl alcohol,polyethylene terephthalate and nylon, and wherein said second tie layeris modified low density polyethylene resin or modified polyethyleneresin when the skin coat layer is either ethyl vinyl alcohol or nylon,and wherein said second tie layer is modified low density polyethyleneresin when said skin coat layer is polyethylene terephthalate.